Microporous membranes, methods for making these membranes, and the use of these membranes as battery separator films

ABSTRACT

A membrane includes a first polyethylene having an Mw&lt;1.0×10 6 , a second polyethylene having an Mw≧1.0×10 6 , and a polypropylene having an Mw≧5.0×10 5  and a ΔHm 80.0 J/g; wherein (a) the sum of the amounts of (i) polypropylene having an Mw≧5.0×10 5  and a ΔHm 80.0 J/g, and (ii) the second polyethylene is≧15.0 wt. %, the weight percents being based on the total weight of the polymer in the membrane; (b) the membrane has a thickness≦12.0 μm; and (c) the membrane is microporous.

RELATED APPLICATION

This patent application claims the benefit of U.S. ProvisionalApplication No. 61/313,970, filed Mar. 15, 2010. This earlierprovisional application is hereby incorporated by reference.

TECHNICAL FIELD

This disclosure relates to microporous membranes having high meltdowntemperature and high strength. The disclosure also relates to theproduction of these membranes and the use of these membranes as batteryseparator films.

BACKGROUND

Microporous membranes are useful as battery separator film (“BSF”) forprimary and secondary batteries. These batteries include lithium ionsecondary batteries, lithium ion polymer secondary batteries,nickel-hydrogen batteries, nickel-cadmium batteries, nickel-zincbatteries, silver-zinc batteries, etc.

Microporous polymeric membranes can be used as battery separator film(“BSF”) in, e.g., lithium ion batteries. Lithium ion batteries in whichthe electrolyte is a gel electrolyte or polymeric electrolyte, e.g., anelectrolyte that is contained within a polymeric medium, (“lithium ionpolymer batteries”) generally utilize BSFs comprising a polymercompatible with (e.g., has affinity for) the polymeric medium in whichthe electrolyte is contained. BSFs for lithium ion polymer batteriesgenerally have a significantly smaller thickness compared to BSFscommonly used in, e.g., cylindrical and prismatic-format lithium ionbatteries.

BSFs comprising polymer have increased polymer mobility at elevatedbattery temperature, which leads to a significant permeability decrease.This effect is beneficial in BSFs because the permeability decrease atelevated temperature results in a decrease in battery electrochemicalactivity, thereby lessening the risk of battery failure underovercharge, rapid-discharge, or other high-temperature batteryconditions. Since battery internal temperature can continue to increaseeven at reduced electrochemical activity (e.g., from temperatureovershoot), it is desirable to increase membrane thermal stability atelevated temperature to further lessen the risk of battery failure. Thiscan be accomplished by including a high melting-point species (e.g.,polypropylene) in the membrane's polymer to increase the BSFs meltdowntemperature to a value≧145° C. The temperature difference betweenpolyethylene and polypropylene melting points and their physicalincompatibility leads to difficulties in producing membranes containingboth polymers, particularly when the membrane is thin, as is the case inlithium ion polymer batteries.

Another important BSF property is the BSFs resistance to pin puncture(commonly referred to as the BSFs “pin puncture strength”). Since BSFpin puncture strength is proportional to BSF thickness for BSFs ofsubstantially the same composition and porosity, batteries utilizingthin BSFs such as lithium ion polymer batteries benefit when the BSF hasa relatively high pin puncture strength per unit thickness. It isdesired, therefore, to produce a relatively thin, high strengthpolymeric membrane having a relatively high meltdown temperature.

SUMMARY

We provide membranes comprising a first polyethylene having anMw<1.0×10⁶, a second polyethylene having an Mw≧1.0×10⁶, and apolypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g; wherein (a) thesum of the amounts of (i) polypropylene having an Mw≧5.0×10⁵ and a ΔHm80.0 J/g and (ii) the second polyethylene is≧15.0 wt. %, the weightpercents being based on the total weight of the polymer in the membrane;(b) the membrane has a thickness≦12.0 μm; and (c) the membrane ismicroporous.

We also provide processes for producing microporous membranes,comprising:

-   -   (1) extruding a mixture of diluent and polymer to form an        extrudate, the polymer comprising a first polyethylene having an        Mw<1.0×10⁶, a second polyethylene having an Mw≧1.0×10⁶, and a        polypropylene having an Mw≧5.0×10⁵ and a ΔHm≧80.0 J/g; wherein        the sum of the amounts of the polypropylene having an Mw≧5.0×10⁵        and a ΔHm 80.0 J/g and the second polyethylene is≧15.0 wt. %,        all the weight percents being based on the total weight of the        polymer in the mixture;    -   (2) processing the extrudate into a microporous membrane having        a thickness≦12.0 μm.

We further provide batteries comprising an anode, a cathode, andelectrolyte, and a battery separator located between the anode and thecathode, the battery separator comprising a membrane comprising a firstpolyethylene having an Mw<1.0×10⁶, a second polyethylene having anMw≧1.0×10⁶, and a polypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g;wherein (a) the sum of the amounts of (i) the polypropylene having anMw≧5.0×10⁵ and a ΔHm 80.0 J/g and (ii) the second polyethylene is≧15.0wt. %, the weight percents being based on the total weight of thepolymer in the membrane; (b) the membrane has a thickness≦12.0 μm; and(c) the membrane is microporous.

DETAILED DESCRIPTION

While producing microporous membranes comprising polyethylene andpolypropylene, we observed that increasing the amount of polypropylenein the membrane increased the membrane's meltdown temperature, butdecreased film yield, particularly in thin membranes, as a result offilm tearing during membrane stretching. Reducing the amount of membranestretching resulted in greater yield, but led to a decrease in themembrane's normalized pin puncture strength to a value that is less thanthe desired value of 3.20×10² mN/μm for BSFs having a thickness≦12.0 μm.We discovered that this difficulty can be overcome when the membranecomprises≦85.0 wt. % of a first polyethylene having a weight averagemolecular weight (“Mw”)≦1.0×10⁶, a second polyethylene having anMw≧1.0×10⁶, and a polypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g,wherein membrane includes≧15.0 wt. % of the second polyethylene and thepolypropylene, the weight percents being based on the total weight ofthe polymer within the membrane. Since relatively high pin puncturestrength is observed even without membrane stretching when the combinedamount of polypropylene and second polyethylene is≧15.0 wt. %,relatively thin membranes (thickness≦12.0 μm) having higher meltdowntemperatures and pin puncture strength can be produced at higher yield.

For the purpose of this description and the appended claims, the term“polymer” means a composition including a plurality of macromolecules,the macromolecules containing recurring units derived from one or moremonomers. The macromolecules can have different size, moleculararchitecture, atomic content and the like. The term “polymer” includesmacromolecules such as copolymer, terpolymer and the like.“Polyethylene” means polyolefin containing≧50% (by number) recurringethylene-derived units, preferably polyethylene homopolymer and/orpolyethylene copolymer wherein at least 85% (by number) of the recurringunits are ethylene units. “Polypropylene” means polyolefincontaining>50.0% (by number) recurring propylene-derived units,preferably polypropylene homopolymer and/or polypropylene copolymerwherein at least 85% (by number) of the recurring units are propyleneunits. The term isotactic polypropylene means polypropylene having ameso pentad fraction≧about 50.0 mol. % mmmm pentads, preferably≧96.0mol. % mmmm pentads (based on the total number of moles of isotacticpolypropylene). A “microporous membrane” comprises a thin film havingpores, where≧90.0 percent (by volume) of the film's pore volume residesin pores having average diameters in the range of from 0.01 μm to 10.0μm. With respect to membranes produced from extrudates, the machinedirection (“MD”) is defined as the direction in which an extrudate isproduced from a die. The transverse direction (“TD”) is defined as thedirection perpendicular to both MD and the thickness direction of theextrudate. MD and TD can be referred to as planar directions of themembrane, where the term “planar” in this context means a directionlying substantially in the plane of the membrane when the membrane isflat.

Polymer Characteristics First Polyethylene (PE1)

The first polyethylene (“PE1”) may generally be characterized by aweight average molecular weight (“Mw”)<1.0×10⁶. The first polyethylenemay include a mixture or reactor blend of polyethylenes, such as amixture of two or more polyethylenes (“PE1a” and “PE1b” and the like, asdescribed below).

PE1a

The first polyethylene (“PE1”) can be, e.g., a polyethylene (PE1a)having an Mw<1.0×10⁶, e.g., in the range of from about 1.0×10⁵ to about0.90×10⁶; a molecular weight distribution (“MWD” defined as Mw dividedby the number average molecular weight)≦50.0, e.g., in the range of fromabout 2.0 to about 20.0; and a terminal unsaturation amount<0.20 per1.0×10⁴ carbon atoms. Optionally, PE1a has an Mw in the range of fromabout 4.0×10⁵ to about 5.0×10⁵, and an MWD of from about 3.0 to about10.0. Optionally, PE1a has an amount of terminal unsaturation≦0.20 per1.0×10⁴ carbon atoms, or 0.14 per 1.0×10⁴ carbon atoms, or≦0.12 per1.0×10⁴ carbon atoms, e.g., in the range of 0.05 to 0.14 per 1.0×10⁴carbon atoms (e.g., below the detection limit of the measurement).

PE1b

The first polyethylene (“PE1”) can be, e.g., polyethylene (PE1b) havingan Mw<1.0×10⁶, e.g., in the range of from about 2.0×10⁵ to about0.9×10⁶, an MWD≦50.0, e.g., in the range of from about 2 to about 50,and a terminal unsaturation amount≧0.20 per 1.0×10⁴ carbon atoms.Optionally, PE1b has an amount of terminal unsaturation≧0.30 per 1.0×10⁴carbon atoms, or≧0.50 per 1.0×10⁴ carbon atoms, e.g., in the range of0.6 to 10.0 per 1.0×10⁴ carbon atoms. A non-limiting example of PE1b isone having an Mw in the range of from about 3.0×10⁵ to about 8.0×10⁵,for example about 7.5×10⁵, and an MWD of from about 4 to about 15.

PE1 can be, e.g., an ethylene homopolymer or an ethylene/α-olefincopolymer containing≧5.0 mole % of one or more comonomer such asα-olefin, based on 100% by mole of the copolymer. Optionally, theα-olefin is one or more of propylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, orstyrene. PE1 can have a melting point≧132° C. PE1a can be produced,e.g., in a process using a Ziegler-Natta or single-site polymerizationcatalyst, but this is not required. The amount of terminal unsaturationcan be measured in accordance with the procedures described in PCTPublication WO 97/23554, for example, the subject matter of which isincorporated herein by reference. PE1b can be produced using achromium-containing catalyst, for example.

Second Polyethylene (PE2)

The second polyethylene (“PE2”) can be, e.g., a polyethylene having anMw≧1.0×10⁶, e.g., in the range of from about 1.0×10⁶ to about 5.0×10⁶and an MWD of from about 1.2 to about 50.0. A non-limiting example ofPE2 is one having an Mw of from about 1.0×10⁶ to about 3.0×10⁶, forexample about 2.0×10⁶, and an MWD≦20.0, e.g., of from about 2.0 to about20.0, preferably about 4.0 to about 15.0. PE2 can be, e.g., an ethylenehomopolymer or an ethylene/α-olefin copolymer containing 5.0 mole % ofone or more comonomers such as α-olefin, based on 100% by mole of thecopolymer. The comonomer can be, for example, one or more of, propylene,butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinylacetate, methyl methacrylate, or styrene. These polymers or copolymerscan be produced using a Ziegler-Natta or a single-site catalyst, thoughthis is not required. PE2 can have a melting point≧134° C. The meltingpoints of PE1 and PE2 can be determined using the methods disclosed inPCT Patent Publication No. WO 2008/140835, for example, the subjectmatter of which is incorporated herein by reference.

Polypropylene (PP)

The polypropylene (“PP”) can be, e.g., polypropylene having anMw≧5.0×10⁵, such as≧6.0×10⁵ or≧7.5×10⁵, for example in the range of fromabout 0.8×10⁶to about 3.0×10⁶, such as in the range of from 0.9×10⁶ to2.0×10⁶. Optionally, the PP has a Tm≧160.0° C. and a ΔHm≧80.0 J/g,e.g.,≧90.0 J/g or≧100.0 J/g, such as in the range of from 110 J/g to 120J/g. Optionally, the PP has an MWD≦20.0, e.g., in the range of fromabout 1.5 to about 10.0, such as in the range of from about 2.0 to about8.5. Optionally, the PP is a copolymer (random or block) of propyleneand≦5.0 mole % of a comonomer, the comonomer being, e.g., one or morea-olefins such as ethylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, styreneand the like; or diolefins such as butadiene, 1,5-hexadiene,1,7-octadiene, 1,9-decadiene and the like.

The PP may be isotactic polypropylene. The PP may have (a) a meso pentadfraction≧about 90.0 mol. % mmmm pentads, optionally≧96.0 mol. % mmmmpentads, preferably≧96.0 mol. % mmmm pentads; and (b) may have an amountof stereo defects≦about 50.0 per 1.0×10⁴ carbon atoms, e.g.,≦about 20per 1.0×10⁴ carbon atoms, or≦about 10.0 per 1.0×10⁴ carbon atoms, suchas≦about 5.0 per 1.0×10⁴ carbon atoms. Optionally, the PP may have oneor more of the following properties: (i) a Tm≧162.0° C.; (ii) anelongational viscosity≧about 5.0×10⁴ Pa sec at a temperature of 230° C.and a strain rate of 25 sec⁻¹; (iii) a Trouton's ratio≧about 15 whenmeasured at a temperature of about 230° C. and a strain rate of 25sec⁻¹; (iv) a Melt Flow Rate (“MFR;” ASTM D-1238-95 Condition L at 230°C. and 2.16 kg)≦about 0.1 dg/min, e.g.,≦about 0.01 dg/min (i.e., a valueis low enough that the MFR is essentially not measurable); or (v) anamount extractable species (extractable by contacting the PP withboiling xylene)≦0.5 wt. %, e.g.,≦0.2 wt. %, such as≦0.1 wt. % or lessbased on the weight of the PP.

The PP may be an isotactic PP having an Mw in the range of from about0.9×10⁶ to about 2.0×10⁶, an MWD 8.5, e.g., in the range of from 2.0 to8.5, e.g., in the range of from 2.5 to 6.0, and a ΔHm≧90.0 J/g.Generally, such a PP has a meso pentad fraction≧94.0 mol. % mmmmpentads, an amount of stereo defects≦about 5.0 per 1.0×10⁴ carbon atoms,and a Tm≧162.0° C.

A non-limiting example of the PP, and methods for determining the PP'sTm, meso pentad fraction, tacticity, intrinsic viscosity, Trouton'sratio, stereo defects, and amount of extractable species are describedin PCT Patent Publication No. WO 2008/140835.

The PP's ΔHm, is determined by the methods disclosed in PCT PatentPublication No. WO 2007/132942, the subject matter of which isincorporated by reference herein. Tm can be determined from differentialscanning calorimetric (DSC) data obtained using a PerkinElmerInstrument, model Pyris 1 DSC. Samples weighing approximately 5.5-6.5 mgare sealed in aluminum sample pans. The DSC data are recorded by firstheating the sample from 25° C. to 230° C. at a rate of 10° C./minute,called first melt (no data recorded). The sample is kept at 230° C. for10 minutes before a cooling-heating cycle is applied. The sample is thencooled from about 230° C. to about 25° C. at a rate of 10° C./minute,called “crystallization,” then kept at 25° C. for 10 minutes, and thenheated to 230° C. at a rate of 10° C./minute, called (“second melt”).The thermal events in both crystallization and second melt are recorded.The melting temperature (T_(m)) is the peak temperature of the secondmelting curve and the crystallization temperature (T_(c)) is the peaktemperature of the crystallization peak.

Microporous Membrane Composition

This description is not meant to foreclose other examples within thebroader scope of this disclosure. The membranes may include an amount A₁of a first polyethylene, an amount A₂ of a second polyethylene, and anamount A₃ of a polypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g.A₁, A₂, and A₃ can be expressed as weight percents, based on the weightof polymer in the membrane. For example, the weight percents can bebased on the combined weight of the first and second polyethylenes andthe polypropylene in the membrane, e.g., A₁+A₂+A₃=100.0 wt. %. Theweight percents can be based on the weight of the membrane, e.g., as canbe the case when the membrane consists essentially of (or even consistsof) the first and second polyethylenes and polypropylene only.

For example, the membrane may include an amount A₁ of the firstpolyethylene (PE1), where A≦85.0 wt. %, an amount A₂ of the secondpolyethylene (PE2), and an amount A₃ of the polypropylene having an 10⁵and a ΔHm 80.0 J/g, where the sum of A₂ and A₃≧15.0 wt. %, the weightpercents being based on the total weight of the polymer within themembrane. In other words, the sum of A₂ and A₃ may be an amount B₁, andB₁≧15.0 wt. %, the weight percents being based on the total weight ofthe polymer within the membrane.

The amount A₁ of the first polyethylene (PE1) may be in the range of70.0 wt. %≦A₁≦85.0 wt. %, the weight percent being based on the totalweight of the polymer in the membrane. Optionally, A₁ may be in therange of 72.0 wt. %≦A₁≦84.0 wt. %, e.g., in the range of 75.0 wt. % to83.0 wt. %, based on the total weight of polymer in the membrane.

The amount A₂ of the second polyethylene (PE2) may be in the range of1.0 wt. %≦A₂≦19.0 wt. %, the weight percent being based on the totalweight of the polymer in the membrane. Optionally, A₂ may be in therange of 3.0 wt. %≦A₂≦15.0, e.g., in the range of 5.0 wt. % to 13.0 wt.%, based on the total weight of polymer in the membrane.

The amount A₃ of polypropylene (PP) may be in the range of 1.0 wt.%≦A₃≦15.0 wt. %, the weight percent being based on the total weight ofthe polymer in the membrane. Optionally, A₃ may be in the range of 3.0wt. %≦A₃≦15.0, e.g., in the range of 5.0 wt. % to 13.0 wt. %, based onthe total weight of polymer in the membrane.

The sum of (i) the amount A₂ of the second polyethylene (PE2) and (ii)the amount A₃ of the polypropylene (PP) may be an amount B₁ in the rangeof 15.0 wt. %≦B₁≦30.0 wt. %, the weight percent being based on the totalweight of the polymer in the membrane. Optionally, B₁ may be in therange of 16.0 wt. %≦B₁≦28.0, e.g., in the range of 17.0 wt. % to 25.0wt. %, based on the total weight of polymer in the membrane.

In an example particularly useful as a BSF for lithium ion polymerbatteries, a membrane comprises 79.0 wt. % to 81.0 wt. % of PE1a, 14.0wt. % to 16.0 wt. % of PE2, and 3.0 wt. % to 7.0 wt. % of PP, wherein(i) the PE1a has an Mw in the range of from about 4.0×10⁵ to about6.0×10⁵, an MWD of from about 3.0 to about 10.0, an amount of terminalunsaturation≦0.14 per 1.0×10⁴ carbon atoms, and a melting point≧132° C.;(ii) the PE2 has an Mw in the range of from about 1.0×10⁶ to about3.0×10⁶, an MWD in the range of from about 4.0 to about 15.0, and amelting point≧134° C.; (iii) the PP is an isotactic PP having an Mw inthe range of from about 0.9×10⁶ to about 2.0×10⁶, an MWD≦8.5, e.g., inthe range of from 2.0 to 8.5, e.g., in the range of from 2.5 to 6.0, anda ΔHm≧90.0 J/g, e.g.,≧100.0 J/g (the weight percents being based on theweight of the membrane); (iv) the membrane is microporous; and (v) themembrane has a thickness≦12.0 μm, such as≦8.0 μm. Optionally, themembrane contains≦1.0 wt. % of PE1b based on the weight of the membrane.Such a membrane has, e.g., a meltdown temperature≧145.0° C.,e.g.,≧150.0° C., and a Normalized Pin Puncture Strength≦3.2×10² mN/μm,e.g.,≧3.3×10² mN/μm. A Normalized Pin Puncture Strength≧3.20×10² mN/μmcan be accomplished in membranes produced by extrusion without the needfor membrane stretching after diluent removal. Optionally, the combinedweight of the PE1a, PE2, and PP is≧95.0 wt. %, e.g.,≧98.0 wt. %, suchas≧99.0 wt. % of the weight of the membrane. Optionally, the membrane isa monolayer membrane.

Other Species

Optionally, inorganic species (such as species containing silicon and/oraluminum atoms, e.g., silica and/or alumina), and/or heat-resistantpolymers such as those described in PCT Publications WO 2007/132942 andWO 2008/016174 (the subject matter of which is incorporated by referenceherein) can be present in the membrane. The membrane may contain≦1.0 wt.% of such materials, based on the weight of the membrane.

A small amount of diluent or other species, e.g., as processing aids,can also be present in the membrane, generally in amounts≦1.0 wt. %based on the weight of the membrane.

When the microporous membrane is produced by extrusion, the finalmicroporous membrane generally comprises the polymer used to produce theextrudate. A small amount of diluent or other species introduced duringprocessing can also be present, generally in amounts less than 1 wt. %based on the weight of the membrane. A small amount of polymer molecularweight degradation might occur during processing, but this isacceptable. In a form, molecular weight degradation during processing,if any, causes the value of MWD of the polymer in the membrane to differfrom the MWD of the polymer used to produce the membrane (e.g., beforeextrusion) by no more than, e.g., about 10%, or no more than about 1%,or no more than about 0.1%.

Mw and MWD Determination

Polymer Mw and MWD can be determined using a High Temperature SizeExclusion Chromatograph, or “SEC,” (GPC PL 220, Polymer Laboratories),equipped with a differential refractive index detector (DRI). Themeasurement is made in accordance with the procedure disclosed in“Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001),” the subjectmatter of which is incorporated herein by reference. Three PLgel Mixed-Bcolumns (available from Polymer Laboratories) are used for the Mw andMWD determination. For PE, the nominal flow rate is 0.5 cm³/min; thenominal injection volume is 300 μL; and the transfer lines, columns, andthe DRI detector are contained in an oven maintained at 145° C. For PP,the nominal flow rate is 1.0 cm³/min; the nominal injection volume is300 μL; and the transfer lines, columns, and the DRI detector arecontained in an oven maintained at 160° C.

The GPC solvent used is filtered Aldrich reagent grade1,2,4-Trichlorobenzene (TCB) containing approximately 1000 ppm ofbutylated hydroxy toluene (BHT). The TCB is degassed with an onlinedegasser prior to introduction into the SEC. The same solvent is used asthe SEC eluent. Polymer solutions are prepared by placing dry polymer ina glass container, adding the desired amount of the TCB solvent, andthen heating the mixture at 160° C. with continuous agitation for about2 hours. The concentration of polymer solution is 0.25 to 0.75 mg/ml.Sample solutions are filtered off-line before injecting to GPC with 2 μmfilter using a model SP260 Sample Prep Station (available from PolymerLaboratories).

The separation efficiency of the column set is calibrated with acalibration curve generated using seventeen individual polystyrenestandards ranging in Mp (“Mp” being defined as the peak in Mw) fromabout 580 to about 10,000,000. The polystyrene standards are obtainedfrom Polymer Laboratories (Amherst, Mass.). A calibration curve (logMpvs. retention volume) is generated by recording the retention volume atthe peak in the DRI signal for each PS standard and fitting this dataset to a 2nd-order polynomial. Samples are analyzed using IGOR Pro,available from Wave Metrics, Inc.

Methods for producing the microporous membranes will now be described inmore detail. While our membranes and methods are described in terms of amonolayer membrane produced by extrusion, this disclosure is not limitedthereto, and this description is not meant to foreclose other exampleswithin the broader scope of the disclosure. Membrane Production Method

The microporous membranes can be produced by combining the firstpolyethylene (e.g., PE1), the second polyethylene (e.g., PE2) and thepolypropylene (e.g., PP) (e.g., by dry blending or melt mixing) withdiluent and optional constituents such as inorganic fillers to form amixture and then extruding the mixture to form an extrudate. At least aportion of the diluent may be removed from the extrudate to form themicroporous membrane. For example, a blend of PE1, PE2 and PP can becombined with diluent such as liquid paraffin to form a mixture, withthe mixture being extruded and processed to form a monolayer membranehaving a thickness≦12.0 μm. Additional layers can be applied to theextrudate, if desired, e.g., to provide the finished membrane with a lowshutdown functionality. In other words, monolayer extrudates ormonolayer microporous membranes can be laminated or coextruded to formmultilayered membranes.

The process for producing the membrane may comprise stretching theextrudate in at least one planar direction before diluent removal. Theprocess may optionally further comprise stretching the membrane in atleast one planar direction after diluent removal. The process forproducing the membrane may optionally further comprise steps for, e.g.,removing at least a portion of any remaining volatile species from themembrane at any time after diluent removal, subjecting the membrane to athermal treatment (such as heat setting or annealing) before or afterdiluent removal. Optional steps for, hot solvent treatment,cross-linking with ionizing radiation, a hydrophilic treatment and thelike, as described in PCT Publication WO 2008/016174, can be conductedif desired. Neither the number nor order of the optional steps iscritical.

Producing the Polymer-Diluent Mixture

PE1, PE2, and PP may be introduced with one or more diluents and mixedto form a polymer-diluent mixture. For example, PE1, PE2, and PP can becombined to form a polymer blend, and the blend is combined with diluent(which can be a mixture of diluents, e.g., a solvent mixture) to producea polymer-diluent mixture. Mixing can be conducted in, e.g., an extrudersuch as a reaction extruder. These extruders include, withoutlimitation, twin-screw extruders, ring extruders, and planetaryextruders. Practice of our processes is not limited to the type ofextruder employed. Optional species can be included in thepolymer-diluent mixture, e.g., fillers, antioxidants, stabilizers,and/or heat-resistant polymers. The type and amounts of these optionalspecies can be the same as described in PCT Publications WO 2007/132942;WO 2008/016174; and WO 2008/140835.

The diluent is generally compatible with the polymers used to producethe extrudate. For example, the diluent can be any species orcombination of species capable of forming a single phase in conjunctionwith the resin at the extrusion temperature. Examples of the diluentinclude one or more of aliphatic or cyclic hydrocarbon such as nonane,decane, decalin and paraffin oil, and phthalic acid ester such asdibutyl phthalate and dioctyl phthalate. Paraffin oil with a kineticviscosity of 20-200 cSt at 40° C. can be used, for example. The diluentcan be the same as those described in U.S. Patent Publication Nos.2008/0057388 and 2008/0057389, the subject matter of both of which areincorporated by reference.

The amount A₁ of the first polyethylene (PE1) may be in the range of70.0 wt. %≦A₁≦85.0 wt. %, the weight percent being based on the totalweight of the polymer in the mixture. Optionally, A₁ may be in the rangeof 72.0 wt. %≦A₁≦84.0 wt. %, e.g., in the range of 75.0 wt. % to 83.0wt. %, based on the total weight of polymer in the mixture. The amountA₂ of the second polyethylene (PE2) may be in the range of 1.0 wt.%≦A₂≦19.0 wt. %, the weight percent being based on the total weight ofthe polymer in the mixture. Optionally, A₂ may be in the range of 3.0wt. %≦A₂≦15.0, e.g., in the range of 5.0 wt. % to 13.0 wt. %, based onthe total weight of polymer in the mixture. The amount A₃ ofpolypropylene (PP) may be in the range of 1.0 wt. %≦A₃≦15.0 wt. %, theweight percent being based on the total weight of the polymer in themixture. Optionally, A₃ may be in the range of 3.0 wt. %≦A₃≦15.0, e.g.,in the range of 5.0 wt. % to 12.0 wt. %, based on the total weight ofpolymer in the mixture. The sum of (i) the amount A₂ of the firstpolyethylene (PE1) and (ii) the amount A₃ of the polypropylene (PP) maybe an amount B₁ in the range of 15.0 wt. %≦B₁≦30.0 wt. %, the weightpercent being based on the total weight of the polymer in the mixture.Optionally, B₁ may be in the range of 16.0 wt. %≦B₁≦28.0, e.g., in therange of 17.0 wt. % to 25.0 wt. %, based on the total weight of polymerin the mixture. A₂ may be in the range of 4.75 wt. %≦A₂≦15.25 wt. %.

Optionally, the polymer-diluent mixture may comprise≦45.0 wt. % polymerbased on the weight of the mixture, e.g., in the range of 30.0 wt. % to40.0 wt. %. The balance can be diluent.

The polymer-diluent mixture during extrusion may be exposed to atemperature in the range of 140° C. to 250° C., e.g., 210° C. to 230° C.

Producing the Extrudate

The polymer-diluent mixture may be conducted from an extruder through adie to produce the extrudate. The extrudate should have an appropriatethickness to produce, after the processing steps, a final membranehaving the desired thickness (generally≦12.0 μm). For example, theextrudate can have a thickness in the range of about 1.0 μm to about10.0 μm, or about 3.0 μm to 8.0 μm. The finished membrane may have afinal membrane thickness (after processing)≦12.0 μm, e.g.,≦10.0 μm.

Extrusion is generally conducted with the polymer-diluent mixture in themolten state. When a sheet-forming die is used, the die lip is generallyheated to an elevated temperature, e.g., in the range of 180° C. to 240°C. Suitable process conditions for accomplishing the extrusion aredisclosed in PCT Publications WO 2007/132942 and WO 2008/016174.

If desired, the extrudate can be exposed to a temperature in the rangeof about 10° C. to about 45° C. to form a cooled extrudate. Cooling rateis not particularly critical. For example, the extrudate can be cooledat a cooling rate of at least about 30° C./minute until the temperatureof the extrudate (the cooled temperature) is approximately equal to theextrudate's gelation temperature (or lower). Process conditions forcooling can be the same as those disclosed in PCT Publications No. WO2007/132942; WO 2008/016174; and WO 2008/140835, for example.

Stretching the Extrudate (Upstream Stretching)

The extrudate or cooled extrudate can be stretched in at least onedirection, e.g., in a planar direction such as MD or TD. It is believedthat such stretching results in at least some orientation of the polymerin the extrudate. This orientation is referred to as “upstream”orientation. In upstream stretching (also called “wet” stretching), theextrudate can be stretched by, for example, a tenter method, a rollmethod, an inflation method or a combination thereof, as described inPCT Publication No. WO 2008/016174, for example. The stretching may beconducted monoaxially or biaxially. In the case of biaxial stretching,any of simultaneous biaxial stretching, sequential stretching ormulti-stage stretching (for instance, a combination of the simultaneousbiaxial stretching and the sequential stretching) can be used. Whenbiaxial stretching is used, the amount of magnification need not be thesame in each stretching direction.

The upstream stretching magnification can be, for example, 2 fold ormore, e.g., 3 to 30 fold in the case of monoaxial stretching. In thecase of biaxial stretching, the stretching magnification can be, forexample, 3 fold or more in any direction, namely 9 fold or more, such as16 fold or more, e.g., 25 fold or more, in area magnification. Anexample for this stretching step would include stretching from about 9fold to about 49 fold in area magnification. Again, the amount ofstretching in either direction need not be the same. The magnificationfactor operates multiplicatively on film size. For example, a filmhaving an initial width (TD) of 2.0 cm that is stretched in TD to amagnification factor of 4 fold will have a final width of 8.0 cm.

The stretching can be conducted while exposing the extrudate to atemperature (the upstream stretching temperature) in the range of fromabout the Tcd temperature to Tm, where Tcd and Tm are defined as thecrystal dispersion temperature and melting point of the PE having thelowest melting point among the polyethylenes used to produce theextrudate (generally the PE such as PE1 or PE2). The crystal dispersiontemperature is determined by measuring the temperature characteristicsof dynamic viscoelasticity according to ASTM D 4065. In instances whereTcd is in the range of about 90° C. to about 100° C., the upstreamstretching temperature can be from 90.0° C. to 122.0° C.; e.g., fromabout 108.0° C. to 116.0° C., such as from 110.0° C. to 114.0° C.

When the sample (e.g., the extrudate, dried extrudate, membrane and thelike) is exposed to an elevated temperature, this exposure can beaccomplished by heating air and then conveying the heated air intoproximity with the sample. The temperature of the heated air, which isgenerally controlled at a set point equal to the desired temperature, isthen conducted toward the sample through a plenum for example. Othermethods for exposing the sample to an elevated temperature, includingconventional methods such as exposing the sample to a heated surface,infra-red heating in an oven and the like, can be used with or insteadof heated air.

Diluent Removal

At least a portion of the diluent may be removed (or displaced) from thestretched extrudate to form a dried membrane. A displacing (or“washing”) solvent can be used to remove (wash away, or displace) thediluent, as described in PCT Publication No. WO 2008/016174, forexample.

At least a portion of any remaining volatile species (e.g., washingsolvent) may be removed from the dried membrane after diluent removal.Any method capable of removing the washing solvent can be used,including conventional methods such as heat-drying, wind-drying (movingair) and the like. Process conditions for removing volatile species suchas washing solvent can be the same as those disclosed in PCT PublicationNo. WO 2008/016174, for example.

Optional Stretching the Membrane (Downstream Stretching)

Following removal of at least a portion of the diluent, the membrane isreferred to as a “dried” membrane. The dried membrane can be stretched(called “downstream stretching”) in at least one direction, e.g., MDand/or TD. Downstream stretching can also be referred to as “drystretching” since at least a portion of the diluent has been removed ordisplaced from the membrane. It is believed that such stretching resultsin at least some orientation of the polymer in the membrane. Thisorientation is referred to as downstream orientation. Before downstreamstretching, the dried membrane has an initial size in MD (a first drylength) and an initial size in TD (a first dry width). As used herein,the term “first dry width” refers to the size of the dried membrane inTD prior to the start of downstream stretching. The term “first drylength” refers to the size of the dried membrane in MD prior to thestart of downstream stretching. Tenter stretching equipment of the kinddescribed in WO 2008/016174 can be used, for example.

The dried membrane can be stretched in MD from the first dry length to asecond dry length that is larger than the first dry length by amagnification factor (the “MD dry stretching magnification factor”) inthe range of from about 1.0 to about 1.6, e.g., in the range of 1.1 to1.5. When TD downstream stretching is used, the dried membrane can bestretched in TD from the first dry width to a second dry width that islarger than the first dry width by a magnification factor (the “TDdownstream stretching magnification factor”). Optionally, the TDdownstream stretching magnification factor is≧the MD downstreamstretching magnification factor. The TD downstream stretchingmagnification factor can be in the range of from about 1.1 to about 1.6,e.g., about 1.1 to 1.5. The downstream stretching can be sequential orsimultaneous in MD and TD. When biaxial downstream stretching is used,the downstream stretching can be simultaneous in MD and TD orsequential. When the downstream stretching is sequential, generally MDstretching is conducted first, followed by TD stretching.

In view of the thickness of certain membranes, downstream stretching maybe avoided or minimized. For example, the processing steps that producefilms having a desired thickness are devoid of any step of downstreamstretching. The processing steps may include downstream stretching to amagnification factor of≦1.1,≦1.08,≦1.05, and≦1.03. The process forproducing the membranes may be devoid of downstream stretching.

The downstream stretching can be conducted while exposing the driedmembrane to a temperature (the downstream stretching temperature)≦Tm,e.g., in the range of from about Tcd-20° C. to Tm. The downstreamstretching temperature may be conducted with the membrane exposed to atemperature in the range of from about 70.0° C. to about 135.0° C., forexample, from about 110.0° C. to about 132.0° C., such as from about120.0° C. to about 130.0° C.

The MD downstream stretching magnification may be about 1.0; the TDdownstream stretching magnification is <1.6, e.g., in the range of fromabout 1.05 to about 1.5, such as 1.1 to 1.5; and the downstreamstretching may be conducted while the membrane is exposed to atemperature in the range of about 120.0° C. to about 130.0° C.

The dry stretching rate is not critical. The dry stretching rate maybe >1%/second in the stretching direction (MD or TD), and the rate canbe independently selected for MD and TD stretching. Optionally, thestretching rate may be >2%/second, e.g., >3%/second, such as >10%/second. The stretching rate may be in the range of 2%/second to25%/second. Though not critical, the upper limit of the stretching ratemay generally be <50%/second to prevent rupture of the membrane.Controlled Reduction of the Membrane's Width

Following the downstream stretching, the dried membrane optionally canbe subjected to a controlled reduction in width from the second drywidth to a third dry width, the third dry width being in the range offrom 0.9 times the first dry width to about 1.5 times larger than thefirst dry width. Optionally, the second dry width is in the range of1.25 to 1.35 of the first dry width and the third dry width is in therange of 0.95 to 1.05 of the first dry width. The width reductiongenerally conducted while the membrane is exposed to a temperature Tcd-30° C., but no greater than Tm, e.g., with the membrane exposed to atemperature in the range of from about 70.0° C. to about 135.0° C., forexample, from about 110.0° C. to about 132.0° C., such as from about120.0° C. to about 130.0° C.

Although the temperature to which the membrane is exposed during thecontrolled width reduction can be the same as the downstream stretchingtemperature, this is not required, and the temperature to which themembrane is exposed during controlled width reduction may be≧1.01 timesthe downstream stretching temperature, e.g., in the range of 1.05 timesto 1.1 times. In a form, the decreasing of the membrane's width isconducted while the membrane is exposed to a temperature that≦130.0° C.,the third dry width is in the range of from 0.95 to 1.05 of the firstdry width.

Heat Set

Optionally, the membrane is thermally treated (heat-set) at least oncefollowing diluent removal, e.g., after downstream stretching, thecontrolled width reduction, or both. It is believed that heat-settingstabilizes crystals and makes uniform lamellas in the membrane. In aform, the heat setting is conducted while exposing the membrane to atemperature (the “heat set temperature”) in the range Tcd to Tm, e.g.,in the range of from about 70.0° C. to about 135.0° C., for example,from about 110.0° C. to about 132.0° C., such as from about 120.0° C. toabout 130.0° C. When the membrane is (i) produced by extruding a mixtureof diluent and a polymer blend of PE1a, PE2, and PP; (ii) the sum of PE2and PP is≦20.0 wt. based on the weight of the polymer in the membrane;and (iii) the heat set temperature is≦126.5° C., such as≦126.0° C., itcan be more difficult to produce a membrane having a Normalized PinPuncture Strength≧3.20×10².

Although the heat set temperature can be the same as the downstreamstretching temperature, this is not required. The temperature to whichthe membrane is exposed during heat setting may be≧1.01 times thedownstream stretching temperature, e.g., in the range of 1.05 times to1.1 times. Generally, the heat setting is conducted for a timesufficient to form uniform lamellas in the membrane, e.g., a time≦1000seconds, e.g., in the range of 1 to 600 seconds. The heat setting may beoperated under conventional heat-set “thermal fixation” conditions. Theterm “thermal fixation” refers to heat-setting carried out whilemaintaining the length and width of the membrane substantially constant,e.g., by holding the membrane's perimeter with tenter clips during theheat setting.

Optionally, an annealing treatment can be conducted after the heat-setstep. The annealing is a heat treatment with no load applied to themembrane, and can be conducted by using, e.g., a heating chamber with abelt conveyer or an air-floating-type heating chamber. The annealing mayalso be conducted continuously after the heat-setting with the tenterslackened. During annealing, the membrane can be exposed to atemperature in the range of Tm or lower, e.g., in the range from about60° C. to about Tm −5° C. Annealing is believed to provide themicroporous membrane with improved permeability and strength.

Optional heated roller, hot solvent, crosslinking, hydrophilizing, andcoating treatments can be conducted, if desired, e.g., as described inPCT Publication No. WO 2008/016174.

Membrane Properties

The membrane may be a microporous membrane that is permeable to liquid(aqueous and non-aqueous) at atmospheric pressure. Thus, the membranecan be used as a battery separator, filtration membrane and the like.The membrane is particularly useful as a BSF for a secondary battery,such as a nickel-hydrogen battery, nickel-cadmium battery, nickel-zincbattery, silver-zinc battery, lithium-ion battery, lithium-ion polymerbattery and the like. The disclosure relates to lithium-ion secondarybatteries containing BSF comprising membrane. Such batteries aredescribed in PCT Patent Publication WO 2008/016174. The microporousmembrane may be a monolayer that is useful as a BSF for polymerbatteries such as lithium-ion polymer batteries. As used herein the term“polymer electrolyte” is used in its ordinary sense to refer to theelectrolyte within a polymer battery. Since BSFs for lithium ion polymerbatteries are generally thin (thickness≦12.0 μm), and since membrane pinpuncture strength is generally proportional to membrane thickness (formembranes of the same porosity and composition), BSFs for lithium ionpolymer batteries benefit from a pin puncture strength per unitthickness that is larger than the pin puncture strength per unitthickness of BSFs used in battery types utilizing thicker BSFs, such acylindrical and prismatic lithium ion batteries. Accordingly, it isdesirable that BSFs for lithium ion polymer batteries have a normalizedpin puncture strength≧3.20×10² mN/μm.

The membranes can have one or more of the following properties.

Thickness

The thickness of the final membrane may be≦12.0 μm, or≦10.0 μm, oreven≦8.0 μm, e.g., in the range of about 1.0 μm to about 10.0 μm, suchas in the range of from 4.5 μm to about 9.5 μm or from 6.0 μm to 8.0 μm.The membrane's thickness can be measured, e.g., by a contact thicknessmeter at 1 cm longitudinal intervals over the width of 10 cm, and thenaveraged to yield the membrane thickness. Thickness meters such as aModel RC-1 Rotary Caliper, available from Maysun, Inc., 746-3 Gokanjima,Fuji City, Shizuoka, Japan 416-0946 or a “Litematic” available fromMitsutoyo Corporation, are suitable. Non-contact thickness measurementmethods are also suitable, e.g., optical thickness measurement methods.

Porosity

The membrane's porosity is measured conventionally by comparing themembrane's actual weight to the weight of an equivalent non-porousmembrane of 100% polymer (equivalent in the sense of having the samepolymer composition, length, width, and thickness). Porosity is thendetermined using the formula: Porosity (expressed as apercent)=99%×(w1/w2), where “w1” is the actual weight of the membrane,and “w2” is the weight of an equivalent non-porous membrane (of the samepolymers) having the same size and thickness. The membrane's porositymay be≧20.0%, e.g., in the range of 20.0% to 80.0%.

Normalized Air Permeability

The membrane may have a normalized air permeability of≦50.0 seconds/100cm³/μm, e.g., in the range of from about 10.0 seconds/100 cm³/μm toabout 45.0 seconds/100 cm³/μm, such as from about 15.0 seconds/100cm³/μm to about 40.0 seconds/100 cm³/μm. Since the air permeabilityvalue is normalized to the value for an equivalent membrane having afilm thickness of 1.0 μm, the membrane's air permeability value isexpressed in units of “seconds/100 cm³/1.0 μm.” Normalized airpermeability is measured according to JIS P8117, and the results arenormalized to the permeability value of an equivalent membrane having athickness of 1.0 μm using the equation A=1.0 μm *(X)/T₁, where X is themeasured air permeability of a membrane having an actual thickness T₁and A is the normalized air permeability of an equivalent membranehaving a thickness of 1.0 μm.

Normalized Pin Puncture Strength

The membrane's pin puncture strength is expressed as the pin puncturestrength of an equivalent membrane having a thickness of 1.0 μm and aporosity of 30% and has the units [mN/μm]. Pin puncture strength isdefined as the maximum load measured at ambient temperature when themembrane having a thickness of T₁ is pricked with a needle of 1 mm indiameter with a spherical end surface (radius R of curvature: 0.5 mm) ata speed of 2 mm/second. The pin puncture strength (“S”) is normalized tothe pin puncture strength value of an equivalent membrane having athickness of 1.0 μm and a porosity of 30% using the equation S₂=[30%*1.0μm *(S₁)]/[T₁*(100%−P)], where S₁ is the measured pin puncture strength,S₂ is the normalized pin puncture strength, P is the membrane's measuredporosity, and T₁ is the average thickness of the membrane. Themembrane's normalized pin puncture strength may be≧3.20×10² mN/μm.Optionally, the membrane's normalized pin puncture strength maybe≧3.3×10² mN/μm, e.g.,≧3.4×10² mN/μm, such as in the range of 3.20×10²mN/μm to 4.50×10² mN/μm.

Shutdown Temperature

The microporous membrane's shutdown temperature is measured by themethod disclosed in PCT Publication No. WO2007/052663, the subjectmatter of which is incorporated by reference herein. According to thatmethod, the microporous membrane is exposed to an increasing temperature(5° C./minute) starting at 25° C. while measuring the membrane's airpermeability. The microporous membrane's shutdown temperature is definedas the temperature at which the microporous membrane's air permeability(Gurley Value) first exceeds 1.0×10⁵ secs./100 cm³. The microporousmembrane's air permeability is measured according to JIS P8117 using anair permeability meter (EGO-1T available from Asahi Seiko Co., Ltd.).The shut down temperature is≦136° C., such as in the range of 132.5° C.to 134.5° C.

Meltdown Temperature

The microporous membrane's shutdown temperature is measured using aprocedure similar to the measurement of shutdown temperature. Accordingto this method, the microporous membrane is exposed to an increasingtemperature (5° C./minute) starting at 25° C. while measuring themembrane's air permeability, to a temperature exceeding the membrane'sShutdown temperature. The membrane heating continues, and themicroporous membrane's Meltdown temperature is defined as thetemperature at which the microporous membrane's air permeability (GurleyValue) first decreases to a value of 1.0×10⁵ secs./100 cm³. Themicroporous membrane's air permeability is measured according to JISP8117 using an air permeability meter (EGO-1T available from Asahi SeikoCo., Ltd.). The Meltdown temperature of the membranes may be≧145.0° C.,e.g.,≧150.0° C., such as≧160.0° C. The Meltdown temperature may be inthe range of 150.0° C. to 165° C.

105° C. Heat Shrinkage

The membrane may have a heat shrinkage at 105° C. in at least one planardirection (e.g., MD or TD) of≦10.0% e.g., 5.0%, such as in the range offrom 1.0% to 5.0%. The membrane's shrinkage at 105° C. in MD and TD ismeasured as follows: (i) measure the size of a test piece of microporousmembrane at ambient temperature in both the MD and TD; (ii) equilibratethe test piece of the microporous membrane at a temperature of 105° C.for 8 hours with no applied load; and then (iii) measure the size of themembrane in both the MD and TD. The heat (or “thermal”) shrinkage in MDand TD can be obtained by dividing the result of measurement (i) by theresult of measurement and (ii) expressing the resulting quotient as apercent.

Tensile Strength

The membrane may have an MD and TD tensile strengths each 1.4×10⁵ kPa,e.g., in the range of 1.5×10⁵ kPa to 2.0×10⁵ kPa. Tensile strength ismeasured in MD and TD according to ASTM D-882A.

Our membranes and methods will be described in more detail withreference to Examples below without intention of restricting the scopeof this disclosure.

EXAMPLES Example 1 (1) Preparation of the Polymer-Diluent Mixture

A polymer-diluent mixture is prepared as follows by combining diluentand a polymer blend of a first polyethylene (PE1a), a secondpolyethylene (PE2), and a polypropylene (PP1). The polymer blendcomprises (a) 85.0 wt. % of PE1 having an Mw of 5.6×10⁵, an MWD of 4.0,an amount of terminal unsaturation 0.14 per 1.0×10⁴ carbon atoms, and aTm of 136.0° C. (PE1); (b) 10.0 wt. % of PE2 having a Mw of 1.9×10⁶ ,and MWD of 5.1, and a Tm of 136.0° C.; and (c) 5.0 wt. % of isotactic PPhaving an Mw of 5.3×10⁵ and a ΔHm of 114 J/g, the weight percents beingbased on the weight of the combined polymer (PP1).

Next, the polymer blend is charged into a strong-blending double-screwextruder having an inner diameter of 58 mm and L/D of 42, and liquidparaffin (50 cst at 40° C.) is supplied to the double-screw extruder viaa side feeder. Mixing is conducted at about 220° C. (or as indicated inthe Table) and 320 rpm to produce the polymer-diluent mixture, whichincluded about 37.5 wt. % polymer and 62.5 wt. % diluent (or asindicated in the Table), the weight percents being based on the weightof the polymer-diluent mixture.

(2) Production of Membrane

The polymer-diluent mixture is conducted from the extruder to asheet-forming die, to form an extrudate (in the form of a sheet). Thedie temperature is about 210° C. The extrudate is cooled by contact withcooling rollers controlled at about 20° C. The cooled extrudate issimultaneously biaxially stretched (upstream stretching) at about 112.5°C. (or as indicated in the Table) to a magnification of 5 fold in bothMD and TD by a tenter-stretching machine. The stretched three-layergel-like sheet is then immersed in a bath of methylene chloridecontrolled at 25° C. to remove liquid paraffin to an amount≦1.0 wt. %based on the weight of the liquid paraffin in the polymer-diluentmixture. The membrane is then dried by air flow at room temperature.While holding the size of the membrane substantially constant themembrane is heat-set by exposing the membrane to a heat set temperatureof about 128.0° C. (or as indicated in the Table) for about 10 minutesto produce the final microporous membrane. Notably, those membraneswhere the Table indicates 1.00 Magnification did not undergo downstreamstretching. Selected starting materials, process conditions, andmembrane properties are set out in Table 1.

Examples 2 and 3 and Comparative Examples C1-C6

Example 1 is repeated except as noted in Table 1. Starting materials andprocess conditions are the same as are used in Example 1, except asnoted in the Table. For example, PP1 may be replaced by a polypropylenehaving an Mw of 1.1×10⁶ and a ΔHm of 114 J/g (PP2). Or, PE1a may bereplaced by a PE1b having an Mw=7.46×10⁵, a Tm of 134.0° C., and aterminal unsaturation amount≧0.20 per 1.0×10⁴ carbon atoms (PE2).Example 2 utilizes downstream stretching in TD, to a magnificationfactor of 1.4. Comparative example 6 utilizes downstream stretching inTD, to a magnification factor of 1.2. The downstream stretching in bothcases is conducted at the specified heat set temperature.

TABLE 1 Example No. 1 2 3 PE2 Content (wt. %) 10.0 10.0 15.0 PE1a orPE1b Grade PE1a PE1a PE1a Content (wt. %) 85.0 85.0 80.0 PP Grades PP1PP2 PP2 Content (wt. %) 5.0 5.0 5.0 Sum PE2 and PP 15.0 15.0 20.0Processing Condition Polymer content (wt. %) polymer-diluent mixture37.5 35.0 35.0 Upstream Stretching Temperature (° C.) 112.5 112.5 112.5Downstream stretching and Heat Set Temperature (° C.) 128.0 129.6 126.7Magnification 1.00 1.40 1.00 Properties Average Thickness (m) 6.9 7.67.4 Porosity (%) 28.7 32.1 32.8 Normalized Air Permeability (sec/100cm³/μm) 38.0 34.9 36.3 Normalized Pin Puncture Strength (mN/μm) 326 350334 TD Heat Shrinkage at 105° C. (%) 4.1 3.4 4.5 MD Heat Shrinkage at105° C. (%) 3.4 3.4 4.0 Meltdown Temperature (° C.) >145 >145 150.7 TDTensile (×10⁵ kPa) 1.833 1.558 1.831 MD Tensile (×10⁵ kPa) 1.506 2.0661.515 TD Elongation (%) 197 101 175 MD Elongation (%) 133 156 135Comparative Example No. C1 C2 C3 C4 C5 C6 PE2 Content (wt. %) 18.0 10.030.0 5.0 5.0 5.0 PE1a or PE1b Grade PE1b PE1a PE1a PE1a PE1a PE1aContent (wt. %) 82.0 85.0 70.0 90.0 90.0 90.0 PP Grades NA PP2 NA PP1PP1 PP1 Content (wt. %) 0.0 5.0 0.0 5.0 5.0 5.0 Sum of PE2 18.0 15.030.0 10.0 10.0 10.0 and PP Processing Condition Polymer content (wt. %)polymer-diluent mixture 30.0 35.0 30.0 35.0 37.5 37.5 UpstreamStretching Temperature (° C.) 113.2 112.5 115.0 112.5 112.5 112.5Downstream stretching and Heat Set Temperature (° C.) 126.2 127.5 129.0128.8 128.8 129.8 TD Magnification Factor 1.00 1.00 1.00 1.00 1.00 1.20Properties Average Thickness (m) 7.0 7.3 7.1 7.2 7.2 7.2 Porosity (%)30.8 31.6 28.7 30.3 31.5 31.4 Normalized Air Permeability (sec/100cm³/μm) 35.4 36.6 36.0 37.4 36.6 36.0 Normalized Pin Puncture Strength(mN/μm) 298 310 307 211 295 334 MD Heat Shrinkage at 105° C. (%) 4.9 3.82.0 2.8 3.2 2.8 TD Heat Shrinkage at 105° C. (%) 3.4 2.8 2.6 2.9 3.4 3.8Meltdown Temperature (° C.) 146.7 146.6 <145 145.0 145.6 ≧145 TD Tensile(×10⁵ kPa) 1.265 1.489 1.408 1.693 1.782 1.686 MD Tensile (×10⁵ kPa)1.844 1.720 2085 1.418 1.298 1.702 TD Elongation (%) 190 173 184 189 176127 MD Elongation (%) 100 125 116 120 128 134

Examples 1-3 show that thin microporous membranes (e.g.,<12.0 μm thick)having useful meltdown temperature deriving from the presence of PP, canbe prepared with useful strength of lithium ion polymer batteries (e.g.,Normalized Pin Puncture Strength≧3.20×10² mN/μm) even in the absence ofdownstream stretching (Examples 1 and 3). In other words, the data showsthat the presence of both PE2 and PP, in a combined amount≧15.0 wt. % ofthe polymer in the membrane, contributes to increased strength andthereby obviates the need for downstream stretching. This latter aspectis particularly advantageous because downstream stretching of thinmembranes is often problematic and leads to tearing of the membranes,which reduces overall yield. Comparative Examples 1 and 3 show thatwithout PP the membrane's meltdown temperature is undesirably low. Acomparison of Example 1 and Comparative Example 2 shows that forextruded membranes having a combined amount of PP and PE2 equal to about15.0 wt. %, based on the weight of the membrane, the polymer-diluentmixture should have a polymer content≧35.0 wt. %, e.g.,≧37.0 wt. %, forthe membrane to achieve a Normalized Pin Puncture Strength≧3.20×10²mN/μm. Comparative Examples 4, 5, and 6 show that when the combinedamount of PE2 and PP is≦15.0 wt. %, downstream stretching is needed forthe membrane to achieve a Normalized Pin Puncture Strength≧3.20×10²mN/μm.

All patents, test procedures, and other documents cited herein,including priority documents, are fully incorporated by reference to theextent such disclosure is not inconsistent and for all jurisdictions inwhich such incorporation is permitted.

While the illustrative forms disclosed herein have been described withparticularity, it will be understood that various other modificationswill be apparent to and can be readily made by those skilled in the artwithout departing from the spirit and scope of the disclosure.Accordingly, it is not intended that the scope of the claims appendedhereto be limited to the examples and descriptions set forth herein butrather that the claims be construed as encompassing all the features ofpatentable novelty which reside herein, including all features whichwould be treated as equivalents thereof by those skilled in the art towhich this disclosure pertains.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

1. A membrane comprising a first polyethylene having an Mw−1.0×10⁶, asecond polyethylene having an Mw≧1.0×10⁶, and a polypropylene having anMw≧5.0×10⁵ and a ΔHm 80.0 J/g; wherein (a) the sum of the amounts of (i)polypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g, and (ii) thesecond polyethylene is≧15.0 wt. %, the weight percents being based onthe total weight of the polymer in the membrane; (b) the membrane has athickness≦12.0 μm; and (c) the membrane is microporous.
 2. The membraneof claim 1, wherein the polypropylene having an Mw≧5.0×10⁵ and a ΔHm80.0 J/g is present in the membrane in an amount in the range of from1.0 wt. % to 15.0 wt. %, the first polyethylene is present in themembrane in an amount in the range of from 70.0 wt. % to 85.0 wt. %, andthe second polyethylene is present in membrane in an amount in the rangeof from 1.0 wt. % to 19.0 wt. %, all being based on the total weight ofthe polymer in the membrane.
 3. The membrane of claim 1, wherein themembrane has a meltdown temperature≧145.0° C. and an a normalized pinpuncture strength≧3.20×10² mN/μm, and a TD Tensile strength≧1.4×10⁵ kPa.4. The membrane of claim 1, wherein the membrane has porosity in therange of 20% to 80%, a normalized air permeability≦50.0 seconds/100cm³/μm, and a TD 105° C. Heat Shrinkage≦10.0%.
 5. The membrane of claim1, wherein the polypropylene comprises≧90.0 wt. % isotacticpolypropylene having an Mw≧6.0×10⁵, an MWD 8.5 and a ΔHm 90.0 J/g, theweight percent being based on the weight of the polypropylene.
 6. Themembrane of claim 1, wherein the membrane has a 105° C. TD heatshrinkage≦6.0%.
 7. The membrane of claim 1, wherein the firstpolyethylene has an Mw in the range of from 4×10⁵ to 6.0×10⁵ and an MWDin the range of from 3.0 to 10.0, and the second polyethylene has an Mwin the range of from 1.0×10⁶ to 3.0×10⁶ and an MWD≦in the range of from4.0 to 15.0.
 8. The membrane of claim 1, wherein the membrane is amonolayer.
 9. The membrane of claim 8, wherein the first polyethylenehas a terminal unsaturation amount<0.20 per 1.0×10⁴ carbon atoms.
 10. Abattery separator film comprising the membrane of claim
 1. 11. A processfor producing a microporous membrane, comprising: (1) extruding amixture of diluent and polymer to form an extrudate, the polymercomprising a first polyethylene having an Mw<1.0×10⁶, a secondpolyethylene having an Mw≧1.0×10⁶, and a polypropylene having anMw≧5×10⁵ and a ΔHm≧80.0 J/g; wherein the sum of the amounts of thepolypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g and the secondpolyethylene is≧15.0 wt. %, all the weight percents being based on thetotal weight of the polymer in the mixture; and (2) processing theextrudate into a microporous membrane having a thickness≦12.0 μm. 12.The method of claim 11, wherein said step of processing includesstretching the extrudate in at least one planar direction.
 13. Themethod of claim 11, wherein said step of processing includes removing atleast a portion of the diluent from the extrudate.
 14. The method ofclaim 13, wherein said step of processing is devoid of any step ofstretching the extrudate after said step of removing the solvent. 15.The method of claim 13, wherein said step of processing optionallyincludes stretching the extrudate after said step of removing thesolvent to a magnification factor of≦1.1 and excludes any stretching ofthe extrudate after said step of removing the solvent at a magnificationfactor or>1.1.
 16. The method of claim 11, further comprising coolingthe extrudate.
 17. The method of claim 11, further comprising subjectingthe membrane to a thermal treatment.
 18. The method of claim 12, whereinthe stretching of step is conducted biaxially to a magnification factorin the range of from 9-fold to 49-fold in area, while exposing theextrudate to a temperature in the range of 90.0° C. to 125.0° C.
 19. Themethod of claim 11, further comprising removing any remaining volatilespecies from the membrane.
 20. The membrane product of claim
 11. 21. Abattery comprising an anode, a cathode, and electrolyte, and batteryseparator located between the anode and the cathode, the batteryseparator being a membrane comprising a first polyethylene having anMw≦1.0×10⁶, a second polyethylene having an Mw≧1.0×10⁶, and apolypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g; wherein (a) thesum of the amounts of (i) the polypropylene having an Mw≧5.0×10⁵ and aΔHm 80.0 J/g and (ii) the second polyethylene is≧15.0 wt. %, the weightpercents being based on the total weight of the polymer in the membrane;(b) the membrane has a thickness≦12.0 μm; and (c) the membrane ismicroporous.
 22. The battery of claim 21, wherein the battery separatormembrane is a monolayer.
 23. The battery of claim 21, wherein thepolypropylene having an Mw≧5.0×10⁵ and a ΔHm 80.0 J/g is present in themembrane in an amount in the range of from 1.0 wt. % to 15.0 wt. %, thefirst polyethylene is present in the membrane in an amount in the rangeof from 70.0 wt. % to 85.0 wt. %, and the second polyethylene is presentin membrane in an amount in the range of from 1.0 wt. % to 19.0 wt. %,based on the total weight of the polymer in the membrane.
 24. Thebattery of claim 21, wherein the membrane has a meltdowntemperature≧145.0° C. and an a normalized pin puncture strength≧3.20×10²mN/μm, and a TD Tensile strength≧1.4×10⁵ kPa.
 25. An electric vehicle orhybrid electrical vehicle comprising motor means electrically connectedto the battery of claim 24.